EP0096508A1 - Matière réfractaire en magnésie-carbone - Google Patents

Matière réfractaire en magnésie-carbone Download PDF

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Publication number
EP0096508A1
EP0096508A1 EP83302984A EP83302984A EP0096508A1 EP 0096508 A1 EP0096508 A1 EP 0096508A1 EP 83302984 A EP83302984 A EP 83302984A EP 83302984 A EP83302984 A EP 83302984A EP 0096508 A1 EP0096508 A1 EP 0096508A1
Authority
EP
European Patent Office
Prior art keywords
magnesia
weight
graphite
fine powder
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP83302984A
Other languages
German (de)
English (en)
Other versions
EP0096508B1 (fr
Inventor
Sunao Motoya
Jiro Watanabe
Kengo Ohara
Masami Kuroe
Hideaki Nishio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shinagawa Refractories Co Ltd
Shinagawa Rozai Co Ltd
Original Assignee
Shinagawa Refractories Co Ltd
Shinagawa Rozai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shinagawa Refractories Co Ltd, Shinagawa Rozai Co Ltd filed Critical Shinagawa Refractories Co Ltd
Priority to AT83302984T priority Critical patent/ATE14568T1/de
Publication of EP0096508A1 publication Critical patent/EP0096508A1/fr
Application granted granted Critical
Publication of EP0096508B1 publication Critical patent/EP0096508B1/fr
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/013—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon

Definitions

  • the present invention relates to unburned magnesia-caroon refractories comprising fine powder as a major component and having excellent resistance to corrosion and oxidation. More specifically, it relates to an improved magnesia-carbon (hereinafter referred to as MgO-C) refractory particularly appropriate for use in refining operations under severe working conditions.
  • MgO-C magnesia-carbon
  • Refining outside the converter has become commonplace in steel manufacture.
  • a SEA-SKF, VAD, L F, and similar types of ladles arc heating, stirring, and vacuum degasification are carried out. Accordingly, refractories used as lining materials in such ladles are exposed to extremely severe working conditions.
  • the unburned MgO-C refractory according to the present invention has a completely different grain size distribution from unburned M gO-C refractories according to the prior art. It comprises 100 parts by weight of refractory raw materials, the refractory raw materials comprising at most 30 parts by weight of fine grains of magnesia having a grain diameter of approximately 1. 5 to approximately 0.3 mm and at least 70 parts by weight of graphite fine powder and magnesia fine powder, the weight ratio of graphite to magnesia being approximately 2.5 to approximately 0.4, and preferaoly further comprises 1 to 6 parts by weight of an additive, the additive comprising at least one substance selected from the group consisting of aluminium, silicon, B 4 C, and SiC.
  • an aggregate having a maximum particle diameter of 5 mm (with a large percentage of the aggregate having a diameter of 2.38 mm) is normally used.
  • refractory raw materials comprising such a coarse aggregate are subjected to moulding pressure, the aggregate grains come directly into contact with one another and the fine powder portion which fills the spaces between coarse grains of the aggregate is prevented from being compressed, resulting in insufficient compactness.
  • a refractory of great compactness is achieved by limiting the size of the aggregate (if any) to 1.5 mm - 0.3 mm, the diameter of the fine powder portion consequently being limited to at most 0.3 mm.
  • the fine powder portion between the aggregate grains can be fully compressed, and laminations do not occur.
  • unburned bricks having a fine powder structure have considerable burning snrinkage and are lacking in serviceability.
  • the addition of grapnite holds down tnis shrinkage. Because the graphite is able to be fully compressed during moulding, the resulting unburned brick has low air permeability, and oxidation loss of the graphite is prevented.
  • the resistance of the graphite to oxidation may be further increased by the addition of a conventionally- used anti-oxidizing agent comprising at least one substance selected from aluminium, silicon, B 4 C, and SiC.
  • This additive comprises 1 to 6 parts by weight of the unburned refractory per 100 parts by weight of refractory raw materials.
  • Figure 1 shows the results of an experiment measuring the bulk density (used as an index of compactness) of a number of bricks comprising a fine powder.
  • Mixtures containing graphite (having a particle diameter of at most 1 mm) and MgO (having a particle diameter of at most 0.3 mm) in various ratios were prepared and moulded at 1000 kg/cm 2 into standardbricks (230 x 114 x 65 mm).
  • graphite and MgO fine powder used in ratios in accordance with the present invention produced bricks having high compactness.
  • an aggregate having a maximum particle diameter of 5 mm (with a large percentage of the aggregate having a diameter of 2.38 mm) is normally used.
  • refractory raw materials comprising such a coarse aggregate are subjected to moulding pressure, the aggregate grains come directly into contact with one another and the fine powder portion which fills the spaces between coarse grains of the aggregate is prevented from being compressed, resulting in insufficient compactness.
  • a refractory of great compactness is achieved by limiting the size of the aggregate (if any) to 1.5 mm - 0.3 mm, the diameter of the fine powder portion consequently being limited to at most 0.3 mm.
  • the fine powder portion between the aggregate grains can be fully compressed, and laminations do not occur.
  • unburned bricks having a fine powder structure have considerable burning snrinkage and are lacking in serviceability. In the present invention, however, the addition of grapnite holds down this shrinkage. Because the graphite is able to be fully compressed during moulding, the resulting unburned brick has low air permeability, and oxidation loss of the graphite is prevented.
  • the resistance of the graphite to oxidation may be further increased by the addition of a conventionally- used anti-oxidizing agent comprising at least one substance selected from aluminium, silicon, B 4 C, and SiC.
  • This additive comprises 1 to 6 parts by weight of the unburned refractory per 100 parts by weight of refractory raw materials.
  • Figure 1 shows the results of an experiment measuring the bulk density (used as an index of compactness) of a number of bricks comprising a fine powder.
  • Mixtures containing graphite (having a particle diameter of at most 1 mm) and MgO (having a particle diameter of at most 0.3 mm) in various ratios were prepared and moulded at 1000 kg/cm 2 into standardbricks (230 x l14 x 65 mm).
  • graphite and MgO fine powder used in ratios in accordance with the present invention produced bricks having high compactness.
  • specimens were prepared comprising seven different mixtures of graphite and MgO, as shown in Table 1.
  • Table 1 The blends snown in the table were moulded at 1000 kg/cm 2 into standard bricks, using liquid resol resin as a binder, dried at 150°C for 10 hours, and then burned in a reducing atmosphere at 1000°C for 3 hours.
  • Figure 2 shows the apparent porosity of these bricks after drying (the .-. line) and after reduction burning (the X -X line).
  • Specimens No. 1 and 7 had an extremely high apparent porosity, and are therefore unsuitable.
  • tne inventors measured the bulk density of a first, conventional unburned MgO refractory comprising 55% by weight of MgO coarse particles (5.3 - 1.5 mm particle diameter), 20% by weight of MgO fine powder (at most 0.3 mm particle diameter), and 25% by weight of graphite.
  • the refractory as a whole had a bulk density of approximately 2.85 - 2.90.
  • the fine powder portion however, had a bulk density of approximately 2.20 (a figure obtained by subtracting the bulk density of the MgO coarse particles) indicating a low degree of compactness.
  • the bulk density of a second refractory comprising 25% by weignt of MgO (1.5 - 0.3 mm particle diameter), 50% by weight of Mg O fine powder (at most 0.3 mm particle diameter), and 25% by weight of graphite (at most 1.0 mm particle diameter) had a high bulk density of 2.61, indicating extremely high packing of the fine powder portion.
  • the above-described first (conventional) refractory had an air permeability index of.0.096 x 10 -2 cm 3 .cm/cm 2 .cm H 2 O.sec, while the unburned second refractory had a far lower value of 0 . 019 x 10 -2 cm -3 .cm/cm 2 .cm H 2 O.sec. This indicates that the inner structure of the second refractory is extremely minute and.homogeneous. It is also clear that the fine powder structure is effective in providing resistance to corrosion.
  • 50 mm x 50 mm x 50 mm cubes were cut from the above-described unburned MgO-C refractories.
  • the cubes were machined, heated in an oxidizing atmosphere in an electric furnace at 1500° C for 2 ncurs, and then cooled, after which they were cut open in order to measure decarburization depth. While the first (conventional) unburned MgO-C refractory had a decarburization depth of 9 mm, the second unburned MgO-C refractory had a decarburization depth of only 3 mm.
  • the raw materials shown in Table 2 were formed into unburned bricks by moulding at 1000 kg/cm 2 . Moulding was followed by drying at 150°C for 10 hours and reduction burning at 1000°C for 3 hours. After drying and burning, the various properties shown in Table 2 were measured.
  • the completed bricks were then used to line the slagline portion of an A S EA -S K F 90-ton ladle, disposed at the 10th and llth rows of bricks on both the slag line and trunion side.
  • the weight ratio of graphite fine powder to magnesia fine powder was 1:1. After the ladle had been used 22 times using bricks according to the present invention, the dimension of the bricks were measured.
  • the thickness of the bricks according to the present invention decreased by 33 mm from 150 mm to 117 mm.
  • conventional MgO- C bricKs which were used in the same ladle under the same conditions (the content of the conventional bricks is shown in Table 2) had a decrease in thickness of 59 mm from 150 mm to 91 mm, giving clear proof of the increased durability of the MgO-C bricks according to the present invention.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Muffle Furnaces And Rotary Kilns (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Ceramic Products (AREA)
EP83302984A 1982-05-28 1983-05-24 Matière réfractaire en magnésie-carbone Expired EP0096508B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83302984T ATE14568T1 (de) 1982-05-28 1983-05-24 Feuerfestes material mit magnesit-kohlenstoff.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP57089765A JPS58208173A (ja) 1982-05-28 1982-05-28 不焼成マグネシア・カ−ボン耐火物
JP89765/82 1982-05-28

Publications (2)

Publication Number Publication Date
EP0096508A1 true EP0096508A1 (fr) 1983-12-21
EP0096508B1 EP0096508B1 (fr) 1985-07-31

Family

ID=13979791

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83302984A Expired EP0096508B1 (fr) 1982-05-28 1983-05-24 Matière réfractaire en magnésie-carbone

Country Status (8)

Country Link
EP (1) EP0096508B1 (fr)
JP (1) JPS58208173A (fr)
KR (1) KR890000485B1 (fr)
AT (1) ATE14568T1 (fr)
AU (1) AU546368B2 (fr)
CA (1) CA1202332A (fr)
DE (2) DE3360467D1 (fr)
ES (1) ES522763A0 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150092A3 (fr) * 1984-01-17 1986-04-23 Shinagawa Refractories Co., Ltd. Composition réfractaire contenant du carbone
WO1986005481A1 (fr) * 1985-03-19 1986-09-25 Veitscher Magnesitwerke-Actien-Gesellschaft Pise refractaire plastique granuleux contenant du carbone
EP0293600A1 (fr) * 1987-05-07 1988-12-07 VAW Aluminium AG Procédé de préparation d'une pierre réfractaire d'oxyde-carbone
GB2282091A (en) * 1993-09-22 1995-03-29 British Steel Plc Parting material
RU2148049C1 (ru) * 1997-10-30 2000-04-27 Открытое акционерное общество "Комбинат Магнезит" Шпинельно-периклазоуглеродистый огнеупор
EP2947060A4 (fr) * 2013-01-16 2016-07-13 Krosakiharima Corp Brique en magnésie-carbone
EP2952494A4 (fr) * 2013-01-31 2016-07-20 Krosakiharima Corp Brique en magnésie-carbone
CN111333408A (zh) * 2020-03-10 2020-06-26 北京利尔高温材料股份有限公司 一种再生镁铝碳质中间包干式料及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT1564195E (pt) * 2002-10-03 2011-09-19 Pedro Fajardo Sola Tijolo refractário cru contendo grafite para fornos da indústria de cimento e sua utilização
KR101350471B1 (ko) * 2012-12-20 2014-01-15 주식회사 포스코 특수강 주조용 슬라이딩 노즐 플레이트의 내화 조성물
JP6190730B2 (ja) * 2013-01-31 2017-08-30 黒崎播磨株式会社 マグネシアカーボンれんが
JP6194257B2 (ja) * 2013-03-06 2017-09-06 黒崎播磨株式会社 マグネシアカーボンれんが

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442669A (en) * 1966-08-16 1969-05-06 Bethlehem Steel Corp Graphite bearing high mgo mortar
DE2248125A1 (de) * 1972-02-03 1973-09-06 Harima Refractories Co Ltd Verfahren zum herstellen feuerfester formkoerper mit flockengraphit
GB2040911A (en) * 1979-02-09 1980-09-03 Kyushu Refractories Carbon-containing refractory bricks

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442669A (en) * 1966-08-16 1969-05-06 Bethlehem Steel Corp Graphite bearing high mgo mortar
DE2248125A1 (de) * 1972-02-03 1973-09-06 Harima Refractories Co Ltd Verfahren zum herstellen feuerfester formkoerper mit flockengraphit
GB2040911A (en) * 1979-02-09 1980-09-03 Kyushu Refractories Carbon-containing refractory bricks

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 92, no. 24, June 1980, page 261, no. 202502a, Columbus, Ohio, USA & JP - A - 79 163 913 (ASAHI GLASS CO., LTD.) 27-12-1979 *
CHEMICAL ABSTRACTS, vol. 96, no. 18, May 1982, page 332, no. 147855y, Columbus, Ohio, USA & JP - A - 82 03772 (KUROSAKI REFRACTORIES CO., LTD.) 09-01-1982 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150092A3 (fr) * 1984-01-17 1986-04-23 Shinagawa Refractories Co., Ltd. Composition réfractaire contenant du carbone
WO1986005481A1 (fr) * 1985-03-19 1986-09-25 Veitscher Magnesitwerke-Actien-Gesellschaft Pise refractaire plastique granuleux contenant du carbone
EP0293600A1 (fr) * 1987-05-07 1988-12-07 VAW Aluminium AG Procédé de préparation d'une pierre réfractaire d'oxyde-carbone
GB2282091A (en) * 1993-09-22 1995-03-29 British Steel Plc Parting material
RU2148049C1 (ru) * 1997-10-30 2000-04-27 Открытое акционерное общество "Комбинат Магнезит" Шпинельно-периклазоуглеродистый огнеупор
EP2947060A4 (fr) * 2013-01-16 2016-07-13 Krosakiharima Corp Brique en magnésie-carbone
EP2952494A4 (fr) * 2013-01-31 2016-07-20 Krosakiharima Corp Brique en magnésie-carbone
CN111333408A (zh) * 2020-03-10 2020-06-26 北京利尔高温材料股份有限公司 一种再生镁铝碳质中间包干式料及其制备方法

Also Published As

Publication number Publication date
JPS58208173A (ja) 1983-12-03
EP0096508B1 (fr) 1985-07-31
ATE14568T1 (de) 1985-08-15
KR890000485B1 (ko) 1989-03-18
ES8406990A1 (es) 1984-08-16
KR840004701A (ko) 1984-10-24
ES522763A0 (es) 1984-08-16
AU1447583A (en) 1983-12-01
CA1202332A (fr) 1986-03-25
DE3360467D1 (en) 1985-09-05
AU546368B2 (en) 1985-08-29
DE96508T1 (de) 1984-04-12

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